An anionic, tetragonal copper(II) superoxide complex

Patrick J. Donoghue, Aalo K. Gupta, David W. Boyce, Christopher J. Cramer, William B. Tolman

Research output: Contribution to journalArticlepeer-review

78 Scopus citations

Abstract

Insight into copper-oxygen species proposed as intermediates in oxidation catalysis is provided by the identification of a Cu(II)-superoxide complex supported by a sterically hindered, pyridinedicarboxamide ligand. A tetragonal, end-on superoxide structure is proposed based on DFT calculations and UV-vis, NMR, EPR, and resonance Raman spectroscopy. The complex yields a trans-1,2-peroxodicopper(II) species upon reaction with [(tmpa)Cu(CH 3CN)]OTf and, unlike other known Cu(II)-superoxide complexes, acts as a base rather than an electrophilic (H-atom abstracting) reagent in reactions with phenols.

Original languageEnglish (US)
Pages (from-to)15869-15871
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number45
DOIs
StatePublished - Nov 17 2010

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